Direct arylation polymerization (DArP) has gained interest in materials chemistry as a method to synthesize conjugated polymers with minimal use of harsh reagents and additional steps. Traditional DArP conditions do not readily yield ideal polymerization characteristics, including chain-growth and low dispersities. It would be of great utility to advance DArP methodology to become competitive with traditional conjugated polymerization techniques. We have developed conditions for a dual-catalytic Ag-Pd system for the synthesis of poly(3-hexylthiophene) (P3HT) that exhibits chain-growth kinetics, low dispersities, and catalyst chain association by Pd. Specifically, the presence of Ag-carboxylate additives plays a beneficial role in the polymerization as a C-H activating agent, while PEPPSI-iPr is used as the Pd source for C-C coupling. The addition of pyridine is necessary to inhibit Pd-mediated C-H activation in the interest of catalyst orthogonality, which can lower dispersities.